Dual-Cure Polymer Systems

• US 20130277890A1
• Filed: 11/04/2011
• Published: 10/24/2013
• Est. Priority Date: 11/04/2010
• Status: Abandoned Application

• Current Assignee: The Board of Regents of the University of Colorado (University of Colorado System)
• Original Assignee: The Board of Regents of the University of Colorado (University of Colorado System)
• Inventors: Bowman, Christopher, Cramer, Neil, Shandas, Robin, Nair, Devatha
• Application Number:
  US13/820,601
• Publication Number:
  US 20130277890A1
• Time in Patent Office: Days
• US Class Current: 264/496
• CPC Class Codes: A61L 2400/16 Materials with shape-memory or superelastic properties
• CPC Class Codes: A61L 27/14 Macromolecular materials
• CPC Class Codes: A61L 27/50 Materials characterised by their function or physical properties , e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
• CPC Class Codes: C08F 2/00 Processes of polymerisation
• CPC Class Codes: C08F 2/48 by ultraviolet or visible light
• CPC Class Codes: C08G 2280/00 Compositions for creating shape memory
• CPC Class Codes: C08G 75/045 from mercapto compounds and unsaturated compounds
• CPC Class Codes: C08G 75/23 Polyethersulfones
• CPC Class Codes: C08J 2333/14 of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C08J 3/243 Two or more independent types of crosslinking for one or more polymers
• CPC Class Codes: C08J 3/244 Stepwise homogeneous crosslinking of one polymer with one crosslinking system, e.g. partial curing
• CPC Class Codes: C08J 3/28 Treatment by wave energy or particle radiation
• CPC Class Codes: C08L 75/16 having terminal carbon-to-carbon unsaturated bonds
• CPC Class Codes: C08L 81/02 Polythioethers; Polythioether-ethers
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

The present invention includes compositions that are useful to prepare dual-cure shape memory polymer systems. The present invention further provides methods of generating a shape memory polymer, optical device, polymer pad with an imprint, or suture anchor system.

Claims

1. A method of generating a given polymer, comprising the steps of:

providing an initial composition comprising a first polymerizable composition and a second polymerizable composition,

wherein said first polymerizable composition undergoes polymerization when submitted to a first polymerization reaction condition,

wherein said second polymerizable composition undergoes polymerization when submitted to a second polymerization reaction condition, and

wherein said first and second polymerization reaction conditions are orthogonal to each other;

submitting said initial composition to said first polymerization reaction condition to promote polymerization of said first polymerizable composition, thereby forming an intermediate composition; and

,

submitting said intermediate composition to said second polymerization reaction condition to promote polymerization of said second polymerizable composition, thereby forming said given polymer.

2. The method of claim 1, wherein said given polymer is used to prepare at least one material selected from the group consisting of a shape memory polymer, optical material, impression material, and combinations thereof.

3. The method of claim 1, wherein said initial composition comprises

a polymerization photoinitiator, at least one acrylate monomer, and a component selected from the group consisting of:

(a) at least one thiol monomer,

wherein the ratio of the thiol equivalent concentration of said at least one thiol monomer in said initial composition and the acrylate equivalent concentration of said at least one acrylate monomer in said initial composition ranges from about 0.05 to about 0.95; and

,

(b) a mixture of at least one nucleophile monomer and at least one isocyanate monomer,

wherein the ratio of the nucleophile equivalent concentration of said at least one nucleophilic monomer in said initial composition and the isocyanate equivalent concentration of said at least one isocyanate monomer in said initial composition is about 1;

1; and

,

wherein said at least one nucleophile monomer comprises a thiol monomer or alcohol monomer;

wherein said initial composition is shaped into a given shape;

wherein said first polymerization reaction condition promotes a reaction selected from the group consisting of;

(a) a reaction between said at least one acrylate monomer and said at least one thiol monomer, and,

(b) a reaction between said at least one nucleophile monomer and said at least one isocyanate monomer;

wherein said intermediate composition comprises unreacted acrylate monomer;

wherein said second polymerization reaction condition promotes photopolymerization of said unreacted acrylate monomer; and

,

wherein said given polymer has enhanced mechanical properties over said intermediate composition.

4. The method of claim 3, wherein said initial composition further comprises a compound selected from the group consisting of an accelerator, urethane based acrylate, and combinations thereof.

5. The method of claim 3, wherein said at least one thiol monomer is selected from the group consisting of 2,5-dimercaptomethyl-1,4-dithiane, 2,3-dimercapto-1-propanol, 2-mercapto-ethylsulfide, 2,3-(dimercaptoethylthio)-1-mercaptopropane, 1,2,3-trimercaptopropane, ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(2-mercaptoacetate), trimethylolpropane tris(2-mercaptoacetate), 1,6-hexanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, isophorone diurethane thiol, and combinations thereof.

6. The method of claim 3, wherein said at least one acrylate monomer is selected from the group consisting of ethylene glycoldi(meth)acrylate, tetraethyleneglycol-di(meth)acrylate, poly(ethylene glycol)dimethacrylates, the condensation product of bisphenol A and glycidyl methacrylate, 2,2′

-bis[4-(3-methacryloxy-2-hydroxypropoxy)-phenyl]propane, hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, allyl(meth)acrylate trimethylolpropane triacrylate, tricyclodecane dimethanol diacrylate, and combinations thereof.

7. The method of claim 3, wherein said polymerization photoinitiator is selected from the group consisting of 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 1-hydroxycyclohexyl benzophenone, trimethyl-benzoyl-diphenyl-phosphine-oxide, and combinations thereof;

and said photopolymerization is promoted by UV radiation.

8. The method of claim 1, wherein said given polymer is used to prepare an optical device;

wherein said initial composition comprises a polymerization photoinitiator, at least one acrylate monomer, and a component selected from the group consisting of;

(a) at least one thiol monomer,

wherein the ratio of the thiol equivalent concentration of said at least one thiol monomer in said initial composition and the acrylate equivalent concentration of said at least one acrylate monomer in said initial composition ranges from about 0.05 to about 0.95; and

,

(b) a mixture of at least one nucleophile monomer and at least one isocyanate monomer,

wherein the ratio of the nucleophile equivalent concentration of said at least one nucleophilic monomer in said initial composition and the isocyanate equivalent concentration of said at least one isocyanate monomer in said initial composition is about 1;

1; and

,

wherein said at least one nucleophile monomer comprises a thiol monomer or alcohol monomer;

wherein said initial composition is shaped into a given shape;

wherein said first polymerization reaction condition promotes a reaction selected from the group consisting of;

(a) a reaction between said at least one acrylate monomer and said at least one thiol monomer, and,

(b) a reaction between said at least one nucleophile monomer and said at least one isocyanate monomer;

wherein said intermediate composition comprises unreacted acrylate monomer;

wherein refractive index gradients are written into said intermediate composition; and

,

wherein said second polymerization reaction condition promotes photopolymerization of said unreacted acrylate monomer, thereby forming said optical device.

9. The method of claim 8, wherein said initial composition further comprises an accelerator, urethane based acrylate, or a combination thereof.

10. The method of claim 8, wherein said initial composition further comprises at least one high-refractive index acrylate.

11. The method of claim 10, wherein said at least one high-refractive index acrylate comprises 2,4,6-tribromophenyl acrylate.

12. The method of claim 1, wherein said given polymer is used to prepare a polymer pad with a given imprint;

wherein said initial composition comprises a polymerization photoinitiator, at least one acrylate monomer, and a component selected from the group consisting of;

(a) at least one thiol monomer,

wherein the ratio of the thiol equivalent concentration of said at least one thiol monomer in said initial composition and the acrylate equivalent concentration of said at least one acrylate monomer in said initial composition ranges from about 0.05 to about 0.95; and

,

(b) a mixture of at least one nucleophile monomer and at least one isocyanate monomer,

wherein the ratio of the nucleophile equivalent concentration of said at least one nucleophilic monomer in said initial composition and the isocyanate equivalent concentration of said at least one isocyanate monomer in said initial composition is about 1;

1; and

,

wherein said at least one nucleophile monomer comprises a thiol monomer or alcohol monomer;

wherein said initial composition is shaped into a given shape;

wherein said first polymerization reaction condition promotes a reaction selected from the group consisting of;

(a) a reaction between said at least one acrylate monomer and said at least one thiol monomer, and,

(b) a reaction between said at least one nucleophile monomer and said at least one isocyanate monomer;

wherein said intermediate composition comprises unreacted acrylate monomer;

wherein said intermediate composition is pressed into a master pattern block,

wherein said block comprises the negative image of said given imprint; and

,

wherein said second polymerization reaction condition promotes photopolymerization of said unreacted acrylate monomer, thereby forming said given imprint on said polymer pad.

13. The method of claim 12, wherein said initial composition further comprises at least one compound selected from the group consisting of an accelerator and a polymerization photoinitiator.

14. (canceled)

15. A composition comprising at least one component selected from the group consisting of:

(a) an acrylate monomer and at least one thiol monomer,

wherein the ratio of the thiol equivalent concentration of said at least one thiol monomer in said composition and the acrylate equivalent concentration of said at least one acrylate monomer in said composition ranges from about 0.05 to about 0.95;

(b) a mixture of at least one nucleophile monomer and at least one electrophile monomer,

wherein the ratio of the nucleophile equivalent concentration of said at least one nucleophile monomer in said composition and the electrophile equivalent concentration of said at least one electrophile monomer in said composition ranges from about 2;

1 to about 1;

2;

wherein said at least one electrophile monomer comprises an isocyanate monomer or epoxy monomer; and

,

wherein said at least one nucleophile monomer comprises a thiol monomer or alcohol monomer;

(c) at least one thiol monomer and at least one monomer selected from the group consisting of acrylate, methacrylate, acrylamide, methacrylamide, maleimide, acrylonitrile, cyanoacrylate and combinations thereof, further optionally comprising a phosphine;

and,

(d) at least one thiol monomer, at least one acrylate monomer, and at least one ene monomer,

wherein the ratio of said at least one thiol monomer to said at least one acrylate monomer is greater than about 1;

1.

16. The composition of claim 15, wherein said at least one thiol monomer is selected from the group consisting of 2,5-dimercaptomethyl-1,4-dithiane, 2,3-dimercapto-1-propanol, 2-mercapto-ethylsulfide, 2,3-(dimercaptoethylthio)-1-mercaptopropane, 1,2,3-trimercaptopropane, ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(2-mercaptoacetate), trimethylolpropane tris(2-mercaptoacetate), 1,6-hexanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, isophorone diurethane thiol, and combinations thereof.

17. The composition of claim 15, wherein said at least one acrylate monomer is selected from the group consisting of ethylene glycol di(meth)acrylate, tetraethyleneglycol-di(meth)acrylate, poly(ethylene glycol)dimethacrylates, the condensation product of bisphenol A and glycidyl methacrylate, 2,2′

-bis[4-(3-methacryloxy-2-hydroxypropoxy)-phenyl]propane, hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, allyl(meth)acrylate trimethylolpropane triacrylate, tricyclodecane dimethanol diacrylate, and combinations thereof.

18. The composition of claim 15, further comprising at least one compound selected from the group consisting of an accelerator and a polymerization photoinitiator.

21. The composition of claim 15, further comprising a filler.

22. The composition of claim 21, wherein said filler comprises at least one selected from the group consisting of a silica particle, Kevlar veil, PET mesh, fiber mesh, metal mesh, Multi-Walled Carbon NanoTube (MWCNTs), Carbon NanoTube (CNTs), organoclay, clay, alumina, titania, zirconia, carbon, bioglass, hydroxyapatite (HA) particle/mesh, quartz, barium glass, barium salt, titanium dioxide, and combinations thereof.

19. (canceled)

20. The composition of claim 19, wherein said polymerization photoinitiator is selected from the group consisting of 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 1-hydroxycyclohexyl benzophenone, trimethyl-benzoyl-diphenyl-phosphine-oxide, and combinations thereof.